CN102153734A - Method for preparing biodegradable polyester from consumed polyester - Google Patents
Method for preparing biodegradable polyester from consumed polyester Download PDFInfo
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Abstract
The invention discloses a method for preparing biodegradable polyester from consumed polyester. The method comprises the following steps of: reacting the consumed polyester and divalent alcohol under the action of a catalyst at the temperature of between 190 and 250 DEG C to decompose the polyester to a corresponding oligomer by the alcohol; adding aliphatic dibasic acid or esterification derivative of the aliphatic dibasic acid and acid or alcohol of multifunctional groups into the oligomer, and performing esterification reaction at the temperature of between 180 and 240 DEG C to obtain corresponding esterification products; and performing condensation polymerization reaction on the esterification products to obtain biodegradable aliphatic-aromatic copolyester. By the method, the consumed and reclaimed polyester material can be directly converted into a biodegradable polyester material, and a virtuous circle channel is provided for reclamation and utilization of non-degradable polyester white pollutants; and the biodegradable polyester material has excellent mechanical and processing properties.
Description
Technical field
The present invention relates to the preparation method of polyester, especially a kind of method for preparing Biodegradable polyester by post-consumer polyester.
Background technology
Now, the white pollution problems of environment is serious day by day, and wherein most pollution comes from non-degraded polyester (PET) wrapping material that abandon after the consumption.
The technology of much recycling about post-consumer polyester is also arranged at present, for example: the CN00815876 patent disclosure a kind ofly make the method for article by reclaiming the PET material, the principal feature of this method is that the PET material that will reclaim heat in pre-treatment, the dry and granulation of crystallization at high temperature simultaneously.No. 00803627 patent disclosure of CN a kind of pollute the back polyester depolymerization and purification process.No. 00817514 patent disclosure of CN a kind of method of from polyester (polyethylene terephthalate (the PET)) waste material that contains inclusion, separating and reclaiming dimethyl terephthalate (DMT) and ethylene glycol.CN 2007800481279 Patent publish a kind of method that is used for making polyester by consumption back polyester.But all there is high energy consumption in above method, the defective of treatment process cost costliness.The product that makes also belongs to non-degradative plastics, produces secondary pollution, and fails effectively more to remove ground, end solution white pollution problems.
Patent US5292783 and US5446079 have then disclosed by binary acid and aromatic dibasic acid and have obtained block and linear random copolyesters as repeating unit after polycondensation, and this material possesses biodegradability.Wherein, di-carboxylic acid combination is that the binary acid of 5-65% mol ratio and aromatic acid that ratio is the 35-95% mol ratio are formed by ratio, and dibasic alcohol is an aliphatic dihydroxy alcohol.Yet this material can not be applied to the extrusion moulding manufacture field because melt viscosity and melt strength are lower, such as, difficulty is bigger with this material blown film, foaming, curtain coating the time.In addition, this method is not suitable for using polyester (PET) material that abandons after the consumption to do raw material, therefore can not be directly used in the solution white pollution problems.
Summary of the invention
For overcoming above technological deficiency, the invention provides a kind of method by the polyester manufacture Biodegradable polyester that reclaims after the consumption.Polyester material after this method can be directly reclaims consumption be converted into the Biodegradable polyester material, for the recycling of non-degraded polyester white pollution thing provides a benign cycle passage.
Method of the present invention may further comprise the steps:
(a) alcoholysis: in 190-250 ℃ of reaction, making the polyester alcoholysis is corresponding oligopolymer under catalyst action for polyester after the consumption and dibasic alcohol;
(b) esterification: in above-mentioned oligopolymer, add B component 1 and B component 2, under 180-240 ℃, carry out esterification and get corresponding esterification products;
(c) polycondensation: with above-mentioned esterification products under 220-260 ℃ temperature, control reaction system vacuum tightness is less than 100Pa, carries out polycondensation, makes biodegradable fat-aromatic copolyester;
Wherein, described B component 1 is selected from the esterified derivative of aliphatic dibasic acid or aliphatic dibasic acid, and described B component 2 is selected from acid that multitube can roll into a ball or pure.
Polyester after the described consumption is selected from one or more mixtures in polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, the polyether ester.
Polyester beverage bottle, polyester film, trevira that described polyethylene terephthalate reclaims from the consumption back.
Described B component 1 is selected from diprotic acid or its carboxylate that carbonatoms is C4-C18, especially is selected from the one or more kinds of mixtures in Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, hendecane dicarboxylic acid and the carboxylate thereof;
One or more kinds of mixtures in Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, hendecane dicarboxylic acid and the carboxylate thereof.
Described dibasic alcohol is selected from one or more the mixture in straight chain aliphatic dihydroxy alcohol, cyclisation aliphatic dihydroxy alcohol or the aliphatic polyether dibasic alcohol.
Described straight chain aliphatic dihydroxy alcohol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2, the 2-ethyl-2-tertiary butyl-1, ammediol or 2,2,4-trimethylammonium-1, the one or more kinds of mixtures in the 6-hexylene glycol.
Described cyclisation aliphatic dihydroxy alcohol is selected from pentamethylene glycol, 1,4 cyclohexane dimethanol, 1,2-cyclohexanedimethanol, 1, the one or more kinds of mixtures in 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol or the Isosorbide.
Described aliphatic polyether dibasic alcohol is selected from one or more the mixture in tripolymer, polyethylene oxide, poly(propylene oxide), polytetrahydrofuran or the epoxy ethane-epoxy propane interpolymer of dimer that molecular weight ranges is the oxyethane of 500-5000g/mol, oxyethane.
Described B component 2 is selected from the one or more kinds of mixtures in the esterified derivative of glycerine, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol, pyromellitic acid, pyromellitic acid dianhydride, trimesic acid, citric acid or above-claimed cpd.
In the described alcoholysis step, the mol ratio of dibasic alcohol and terephthalic acid group is 0.8-2.00:1.
The catalyzer of described alcoholysis step is selected from one or more the mixture in the organic metal salt of Ti, Ge, La, Ce, Zn, Fe, Mn, Co, V, Zr, Li, Ca or these elements.Preferred organic acid salt and alkoxyl group salt.
The catalyzer of described condensation polymerization step is selected from organic titanium.
20% to 70 % of all acid content is an aliphatic dibasic acid in described biological degradation fat-aromatic polyester
Also, dibasic alcohol is back to reactor in described alcoholysis step, removes by products such as tetrahydrofuran (THF), acetaldehyde simultaneously.
Thermoplastic polyester is the polymkeric substance that is obtained by polycondensation by dibasic alcohol and diprotic acid in the prior art.Via different types of diprotic acid and dibasic alcohol, can synthesize multiple polyester with different characteristics.Commercial principal item mainly contains: polybutylene terephthalate, polyethylene terephthalate, poly terephthalic acid-1,4-hexanaphthene dimethyl ester, PBN and polyester liquid crystalline polymers series, polyarylester, polyester elastomer etc.Different along with polyester kind and manufacturer, also there are difference in its synthesis and preparation process and synthetic method.Usually, production of polyester has two kinds of batch production process and continous way production processes.Basic, polyester synthetic chemical process is basically via esterification stage, transesterification reaction stage, polycondensation stage, different according to polyester kind and synthetic control method, and there are characteristics separately again in the equipment configuration in each stage and processing requirement.
Biodegradable polyester of the present invention belongs to thermoplastic polyester, its preparation method includes the esterification stage, transesterification reaction stage and polycondensation stage, described B component can add in described any one step of reaction, promptly can add in the preceding adding of esterification (being also referred to as transesterification reaction) or after esterification is finished, or before polycondensation or after the polycondensation, add, can also be in the post-production process, to add; Described post-production process such as mechanically mixing processing, the processing of single screw rod or twin screw processing or other existing working methods, preparation method's of the present invention processing condition can be with reference to prior art, as esterification among the preferred version preparation method of the present invention and transesterification reaction phase temperature scope is 150-240 ℃, can carry out under normal pressure, the polycondensation stage can carry out in reduced pressure and 160-250 ℃ of scope.
Can come catalyzed reaction by in reaction process, adding appropriate amount of catalysts when preparing Biodegradable polyester by polycondensation, this class catalyzer is selected from the mixture of stibnide, titanium sub-group compound and these compounds, perhaps uses the material with same function.Catalyst levels is the 50-1000ppm of weight resin.
In polycondensation process, in order to prevent unnecessary degraded and/or branching reaction, can add an amount of stablizer in this reaction process, this class stablizer comprises: phosphoric acid, phosphorous acid, triphenylphosphate, trimethyl phosphite 99, trialkyl phosphite, tricresyl phosphite phenylester, phosphonic acids triphenyl ester, phosphonic acids trialkyl ester.In polycondensation process, also can add the oxidation inhibitor of hindered phenolic, as antioxidant 1010, oxidation inhibitor 168, antioxidant 1076.
The Biodegradable polyester that the present invention relates to can be used for injection moulding, blowing, plastic uptake, curtain coating, field of plastics processing such as wire drawing, and can be at the enterprising line operate of conventional processing units, also can with blend such as other degradative plasticss or plant based material, as poly(lactic acid), polycaprolactone, polyglycolic acid, Succinic Acid/butyleneglycol copolyesters, starch, Mierocrystalline cellulose, vegetable fibre, plant powder etc., also can with the common plastics blend, make the structured material product, sheet material, the film material, foam materials and frame material are applied to packaging industry, carrier, catering industry, the expendable material of industries such as agriculture and animal husbandry production.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention adopts the plastics of the synthetic complete biodegradable of polyethylene terephthalate after the consumption, has both solved the recovery problem of post-consumer polyester, has avoided secondary pollution again, and the simple environmental protection low-carbon (LC) of production technique.
2. the polyester material of the present invention's production has excellent mechanical property and aesthetic appearance, can be used for processing the film forming material.After resistance toheat improves, can also be applied to have the course of processing of long loop cycle, such as the injection moulding course of processing.
Embodiment
Provide embodiment below being described in more detail the present invention, but it is worthy of note that the present invention is not limited to these embodiment, some nonessential change and adjustment that one of skill in the art makes according to the invention described above still belong to protection scope of the present invention.
The testing method of index of correlation is as follows in the embodiment:
1. relative molecular mass testing method: adopt Waters gel chromatography test polymer relative molecular mass, trichloromethane is a moving phase, take-off rate 1mL/ min, and 40 ℃ of temperature, standard is the polystyrene of narrow distribution;
2. characteristic viscosity determining method: 25 ℃ of mensuration, as solvent, adopt the limiting viscosity of determination of ubbelohde viscometer sample with phenol-orthodichlorobenzene mixed solution (mass ratio 3:2), sample concentration is 0.005 g/mL.
3. content of carboxyl end group testing method: (mass ratio 7:3) is solvent with ortho-cresol-trichloromethane mixed solution, adopt Switzerland's ten thousand logical Titrino series automatic potential titrator tests examination content of carboxyl end group, testing method is referring to standard FZ/T 50012-2006 " polyester middle-end carboxyl Content volumetry ".
4. plastics melt temperature testing method: adopt the melt temperature of Perkin Elmer DSC-6 analyser specimen, nitrogen flow rate is 20 mL/min, 10 ℃/min of temperature rise rate.
5. biodegradation test method:, be the degradation property index with CO2 burst size behind 90 days compost of material with reference to the testing method of ISO14855.
Embodiment 1(butyleneglycol)
1; beverage bottle polyethylene terephthalate 35g after 4-butyleneglycol 33g, the consumption joins in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add hexanodioic acid 32g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=36560, Mw=62700, viscosity 1.18dL/g, end carboxyl 30mol/t, 113.8 ℃ of fusing points, degradation rate was calculated as 80% with carbon dioxide releasing amount in 90 days.
Embodiment 2(ethylene glycol, Succinic Acid)
Beverage bottle polyethylene terephthalate 60g after ethylene glycol 25g, the consumption is joined in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 50mg; keeping reactor temperature is 210 ℃; condenser refluxes ethylene glycol, makes polyethylene terephthalate alcoholysis wherein, reacts 3 hours.Add Succinic Acid 20g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=26560, Mw=42700, viscosity 0.8dL/g, end carboxyl 33mol/t, 180.8 ℃ of fusing points, degradation rate was calculated as 40% with carbon dioxide releasing amount in 90 days.
Embodiment 3(Succinic Acid, polyoxyethylene glycol)
Beverage bottle polyethylene terephthalate 60 g after ethylene glycol 33g, cetomacrogol 1000 5g, the consumption are joined in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg; keeping reactor temperature is 210 ℃; condenser refluxes ethylene glycol, makes polyethylene terephthalate alcoholysis wherein, reacts 4 hours.Add Succinic Acid 20g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=28360, Mw=43500, viscosity 0.85dL/g, end carboxyl 30mol/t, 168 ℃ of fusing points, degradation rate was calculated as 52% with carbon dioxide releasing amount in 90 days.
T content increases in the embodiment 4(product)
1; beverage bottle polyethylene terephthalate 65g after 4-butyleneglycol 33g, the consumption joins in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add hexanodioic acid 32g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=32750, Mw=64500, viscosity 1.13dL/g, end carboxyl 25mol/t, 145 ℃ of fusing points, degradation rate was calculated as 55% with carbon dioxide releasing amount in 90 days.
Embodiment 5 (adding branching agent)
1; beverage bottle polyethylene terephthalate 35g after 4-butyleneglycol 33g, the consumption joins in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add hexanodioic acid 32g and TriMethylolPropane(TMP) 0.1g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=39300, Mw=82500, viscosity 1.21dL/g, end carboxyl 30mol/t, 114 ℃ of fusing points, degradation rate was calculated as 75% with carbon dioxide releasing amount in 90 days.
Embodiment 6(increases the butyleneglycol amount)
1; beverage bottle polyethylene terephthalate 65g after 4-butyleneglycol 50g, the consumption joins in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add hexanodioic acid 62g and TriMethylolPropane(TMP) 0.2g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=38570, Mw=58700, viscosity 1.17dL/g, end carboxyl 30mol/t, 114 ℃ of fusing points, degradation rate was calculated as 80% with carbon dioxide releasing amount in 90 days.
Embodiment 7(sebacic acid)
1; beverage bottle polyethylene terephthalate 65g after 4-butyleneglycol 50g, the consumption joins in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add sebacic acid 40g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=36560, Mw=62700, viscosity 1.18dL/g, end carboxyl 30mol/t, 113.8 ℃ of fusing points, degradation rate was calculated as 80% with carbon dioxide releasing amount in 90 days.
Embodiment 8(propylene glycol)
1; beverage bottle polyethylene terephthalate 65g after ammediol 50g, the consumption joins in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 30mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add hexanodioic acid 32g and TriMethylolPropane(TMP) 0.2g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=36560, Mw=62700, viscosity 1.18dL/g, end carboxyl 30mol/t, 113.8 ℃ of fusing points, degradation rate was calculated as 80% with carbon dioxide releasing amount in 90 days.
Comparative Examples 1
1; 4-butyleneglycol 50g, terephthalic acid dioctyl phthalate 35g join in the reactor; under the nitrogen protection; be warming up to 210 ℃; add tetrabutyl titanate 100mg, keeping reactor temperature is 210 ℃, makes polyethylene terephthalate alcoholysis wherein; remove reaction ethylene glycol by shunting simultaneously, reacted 4 hours.Add hexanodioic acid 32g, carry out esterification, judge level of response by the water that the weighing reaction generates, esterification yield reaches at 95% o'clock, after the temperature to 230 ℃, reacted 30 minutes, and began slowly to be warming up to 245 ℃ then, progressively increase vacuum tightness, keep temperature-resistant, keep below the still internal pressure 80Pa, reacted 3.5 hours, promptly get product.
Obtain the product index of correlation: molecular weight: Mn=38730, Mw=65200, viscosity 1.19dL/g, end carboxyl 27mol/t, 115 ℃ of fusing points, degradation rate was calculated as 80% with carbon dioxide releasing amount in 90 days.
By Comparative Examples as can be known, adopt the PET synthetic biodegradable plastic after consuming consistent with the performance and the degradation capability that adopt new starting material synthetic biodegradable plastic.
Claims (10)
1. one kind prepares the method for Biodegradable polyester by post-consumer polyester, may further comprise the steps:
(a) alcoholysis: in 190-250 ℃ of reaction, making the polyester alcoholysis is corresponding oligopolymer under catalyst action for polyester after the consumption and dibasic alcohol;
(b) esterification: in above-mentioned oligopolymer, add B component 1 and B component 2, under 180-240 ℃, carry out esterification and get corresponding esterification products;
(c) polycondensation: with above-mentioned esterification products under 220-260 ℃ temperature, control reaction system vacuum tightness is less than 100Pa, carries out polycondensation, makes biodegradable fat-aromatic copolyester;
Wherein, described B component 1 is selected from the esterified derivative of aliphatic dibasic acid or aliphatic dibasic acid, and described B component 2 is selected from acid that multitube can roll into a ball or pure.
2. according to claims 1 described method, it is characterized in that: the polyester after the described consumption is selected from one or more mixtures in polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, the polyether ester.
3. according to claims 2 described methods, it is characterized in that: polyester beverage bottle, polyester film, trevira that described polyethylene terephthalate reclaims from the consumption back.
4. according to claims 1 described method, it is characterized in that: described B component 1 is selected from the one or more kinds of mixtures in Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, hendecane dicarboxylic acid and the carboxylate thereof.
5. method according to claim 1 is characterized in that: described dibasic alcohol is selected from one or more the mixture in straight chain aliphatic dihydroxy alcohol, cyclisation aliphatic dihydroxy alcohol or the aliphatic polyether dibasic alcohol.
6. method according to claim 5 is characterized in that: described straight chain aliphatic dihydroxy alcohol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 2,2-dimethyl-1, ammediol, the 2-ethyl-2-tertiary butyl-1, ammediol or 2,2,4-trimethylammonium-1, the one or more kinds of mixtures in the 6-hexylene glycol; Described cyclisation aliphatic dihydroxy alcohol is selected from pentamethylene glycol, 1,4 cyclohexane dimethanol, 1,2-cyclohexanedimethanol, 1, the one or more kinds of mixtures in 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol or the Isosorbide; Described aliphatic polyether dibasic alcohol is selected from one or more the mixture in tripolymer, polyethylene oxide, poly(propylene oxide), polytetrahydrofuran or the epoxy ethane-epoxy propane interpolymer of dimer that molecular weight ranges is the oxyethane of 500-5000g/mol, oxyethane.
7. method according to claim 1 is characterized in that: described B component 2 is selected from the one or more kinds of mixtures in the esterified derivative of glycerine, TriMethylolPropane(TMP), tetramethylolmethane, dipentaerythritol, pyromellitic acid, pyromellitic acid dianhydride, trimesic acid, citric acid or above-claimed cpd.
8. method according to claim 1 is characterized in that: the mol ratio of dibasic alcohol and terephthalic acid group is 0.8-2.00:1 during alcoholysis.
9. method according to claim 1, it is characterized in that: the catalyzer of described alcoholysis step is selected from one or more the mixture in the organic metal salt of Ti, Ge, La, Ce, Zn, Fe, Mn, Co, V, Zr, Li, Ca or these elements, and the catalyzer of described condensation polymerization step is selected from organic titanium.
10. by the polyester of the described method preparation of claim 1, it is characterized in that: 20% to 70 % of all acid content is an aliphatic dibasic acid in described biological degradation fat-aromatic polyester.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2095536C (en) * | 1990-11-30 | 1999-02-16 | Charles M. Buchanan | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
| CN1631935A (en) * | 2004-11-18 | 2005-06-29 | 华东理工大学华昌聚合物有限公司 | Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material |
| WO2008085396A1 (en) * | 2006-12-27 | 2008-07-17 | E. I. Du Pont De Nemours And Company | Processes for manufacturing polyesters from post-consumer polyester |
| CN101885838A (en) * | 2009-05-13 | 2010-11-17 | 金发科技股份有限公司 | Bio-degradable polyester and method for preparing same |
-
2010
- 2010-12-30 CN CN2010106133460A patent/CN102153734B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2095536C (en) * | 1990-11-30 | 1999-02-16 | Charles M. Buchanan | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
| CN1631935A (en) * | 2004-11-18 | 2005-06-29 | 华东理工大学华昌聚合物有限公司 | Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material |
| WO2008085396A1 (en) * | 2006-12-27 | 2008-07-17 | E. I. Du Pont De Nemours And Company | Processes for manufacturing polyesters from post-consumer polyester |
| CN101885838A (en) * | 2009-05-13 | 2010-11-17 | 金发科技股份有限公司 | Bio-degradable polyester and method for preparing same |
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